Halogen substituted acylamino sulphonic acids of the aromatic series and their manufacture



,rsanleel v size, 194s "STATES PATENT F HALOGEN SUBSTITUTED ACYLAM'INO SUL-t PHONIC ACIDS OF THE AROMATIC SERIES i AND THEIR MANUFACTURE Henry Martin, Basel, Hans Heinrich Zaeslin,

- UNi'l'Ei).

the products being useful for various Biehen, and Rudolf I-Iirt, Curt Glatthaar, and

Alfred Staub,

Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application June 15,1942, Serial No. 447,180. In Switzerland June 16, 1938 3 (Ci. 269 506) I amino sulphonic acids, with the development of .Ihis application is a continuation-in-part of application Ser. No. 278,954, flied June 13, 1939 (now U.S. Patent No. 2,311,062). r

This invention relates to the production of halogen substituted acyl amino sulphonic acids, purposes in industry e. g. for protecting wool and other substances against damage by moths, the protection being very fast to washing and fuliing, and in some cases as disinfecting agents, bactericides,

- fungicides, and seed, steeping materials.

' According to the present invention halogen substltuted acyl amino sulphonic acids of the arcmatic series are produced by the treatment of carbonic acid derivatives or substances or mixtures of substances forming these compounds which may aisocontain sulphonic acid groups with isocyclic amines or aminosulphonic acids containing replaceable hydrogen at the nitrogen 'phatic, aliphatic-aromatic and aromatic car.-

bamic acid chlorides. Halogen and/or alkyl substituted aromatic and aliphatic-aromatic carbamic acid chlorides larlyvaluable. V 1 I I The condensation products'in question may, however, also be obtained by the addition of isohave proved to be particucyanates, especially of halogenand/or alkylsubstituted aromatic-isocyanic acid esters, to aronitrogen, to urea derivatives. t

In all these methodsthe substitution of the components must be efl'ected in such a manner that at least one halogen atom and one sulphonic acid group are present in the final product. These may be present in either of the reaction components or even in both at the, same time. The carbamic acid chlorides and isocyanic acid esters, used as initial material, can be obtained by the known processes. By treatment of primary or secondary aliphatic, aliphatic-aromatic, aromatic, araliphatic, araliphatic-aromatic amines,

such as aniline, toluidine, 4-chloraniline, 3:4-dichloraniline, 2 5-dlchloraniline, 2 4-dichloraniline, 3-chloro 4 methyl 6 methoxy aniline,

3-chloro-i-methyl-G-ethoxyaniline, 3 :4-dichlor'o- 6-methoxy-aniline, 4-nitraniline, ethylaniline, 4-laurylaniline, laurylphenylamine, diphenylamine, 2 amino 4:4 dichlorodiphenyl ether,

, 4-ch1oro 4-aminodiphenyl-suiphone, 3 :4 5-trichioraniline, 2:4:5-trichloraniline, laurylamine,

a dodecylbenzylamine, etc., with phosgene a sim- Dlereaction produces the carbamic acid chlorides.

By suitable conversion known per se the latter,' obtained from the corresponding primary amines,

can be converted easily intoisocyanic acidester. A aromatic amines there are preferably suitable amino sulphonic acids, for example the su1-' phonic acids of the aminodiphenylmethanes,

aminodiphenylamines, aminobenzanilides. Inthis case there are especially suitable halogen and/or alkyl substituted derivatives of the above mentionedaminoor polyamino-sulphonic acids, such as 3:4-dichloro-4'-aminodiphenylamine 2 sulphonic acid, ,4:4'-dichloro 2 amino 1:1 diphenylmethane-W-sulphonic acid, 4-chloro-4faminodiphenylketone-3rsulphonic acid, 3'-aminobenzoyl-3t4-dichloranilinee6-sulphonic acid;

By a suitable selection oi the substitution it is possible to construct products with one or more matic amino sulphonic acids. Similar bodies are formed by the addition 'ofaromatic carbamic acid-chloride sulphonic acids and isocyanate sul-" phonic acids respectively to suitable; aromatic amines. It will be understood that similar products can be obtained by warming, melting or heating, in suitable solvents orsuspension media,

'- the amino sulphonic acids with urea, with sepstation of ammonia. Furthermore, by sulphonating completely condensed, difliculty soluble or in solublelureaajcontaining at least one halogen atom, sulphonic acids with surprisingly 6 perties carbonic asides lead by condensation with be obtained. 0r alkylor aryl-' sulphonic acids. For example, by the action of phosgene on the above-defined halogenated amino-mon'o-sulphonic acids, there result ureas with two sulphonic acid groups. On the other hand, for example, by the actionof specified carbamic acid chlorides, especially of halogenated, V aliphatic-aromatic carbamic acid chlorides on amino-sulphonic acids, there are formed ureas with one.sulphonic acid group. The invention thus concerns symmetrical and unsymmetrical urea sulphonic acids as well as those which at the, nitrogen appear more or lesscompletely allrylated, aralkylated or arylated.

condensation of aminosulphonic acids or alondary carbamic acid chlorides it is possible to produce di-, .triand tetrasubstituted ureas. By conversion of aminosulphonic acids and akyl aminosulphonic acids with nitro-urea or cyanate.

%example be further condensed with acid chlorides, alkyl chlorides, aldehydes or the like. The condition; however, always remains that after sulphonic acid group are present in the reaction product.

the most cases it the condensations are performed with. the sulphonic-acid-group-free amines and 'taining exchangeable hydrogen at the nitrogen genatediaminodiphenyl methane-sulphonic acids '7 atom there maybe named amongst others haloas particularly convenient.

not or not h hly halogenated acylamino sul phonic acids which are obtained according to the atives or such compounds yieldingsubstancesor aminosulphonic acids having exchangeable hydrogen at the nitrogen atom, one obtains, however, also easily the corresponding halogenation prodareobtainable by use of halogenated amines or eat halogens one obtains new compounds technically not available heretofore.

The herein claimed symmetrical and hair, paper, textiles, leather, natural or artificial from moths and other textile destructive grubs.

also suitable as disinfecting agents,- as bactericury-free seed steeping materials, as valuable of water and the necessary quantity of soda, parts of crystalline sodium acetate are added and phosgene is passed through at -40 C.; until no more amine is present. The paste precipitated The same or similar compounds are obtained in By usual halogenation of completely formed, 1 a on to ice, sucked omwashed with waterm-d I especi y 5 unsymmetrical urea-sulphonic acids are predominantly suitable for protecting wool, feathers, furs,

fibres, or articles containing these substances l The following examples illustratelthe process, 1

10 parts oi-4-amino-4'-chlbro-l:l diphenyl- 1 amine-fl-sulphonic acid, produced by the known process from p-chlor-aniline and p-chloronitro- 1 benzenesulphonic acid, are dissolved in 150 parts I.

/ with acid is separated,converted with sodainto the 1 sodium salt and salted outwltlrcookins sa t. The

kylaminosulphonic'acids with N-primary or sec- 1 there are formed monoand di-substituted un 1 a symmetrical urea derivatives. The latter can for condensation at least one halogen atom and one L above process from reactive carbonic acidderivmixtures of substances and isocyclic aminesor 5 r ucts which are also well adapted for determined 3 purposes. By this means, there are obtainedin part the same acylamino-sulphonic acids as they aminosulphonic acids, in part, however, also substitution products halogenated inother positions. i It is particularly to be noted (that by use or diii'er- 1 soluble in water. The yield is excellent.

Instead oi the above diphenylaininesulphoni acid there may also be used another one as i'or. i

' example 4-amino-3':4f-dichloro-1:1-diphenyl-L amine-z-sulphonic acid" or i-amino-4':6'-di- 1 chloro-l:l'-diphenylamine 2-sulphonic acid.

- v i Example 2 103 parts by stirred with 300 parts by volume oi chlorobenzene and 100 parts 0! aluminium chloride ates.- c. until hydrochloric acid ceases to be formed. The excess chlorobenzene,.ai'ter decomposition of the aluminium chloride with ice is driven oi! steam, the residue isethered out, dried and distilled under reduced pressure. The condense-'- tion product, probably 2-nitro- 4:4' -di chloro-"-- *lrl'Miphenylmethane boils at boiling point 15 dried. The 2 amino- 4:"4' dichlorolfl' -di-,

phenylmethane-2'-sulphonic acid forms a white powder of very sweet taste. 10 parts or this di-. phenylmethane sulphonic acid are dissolved in f 150 parts of water by means of sodaytreated withvthe necessary'quantity oi crystalline sodium acetate and phosgene isintroduced at SID-40 0.. until the azo reaction has disappeared. The

dipiienylmethane urea is precipitated when the solution is exactly neutralised by means of soda.

After drying under reduced pressure it forms a bright powder which-dissolves clear in water.

Emmple 1 16.5 parts ofthe 2-amino-4:1"-dichlorol:l'- diphenyl-methane-2-sulphonic acid, described in Example 2, are dissolved in 100-parts by volume or dry pyridine, and into the solution there are introduced at 10-l5 C., whilst thoroughly 1 stirring, 10 parts of 3:4-dichlorophenylisocyanate insmall portions. -Aiter 1 hour the sac reaction has disappeared, the reaction mixture is then [treated with steam until no fin-the! Pyridine The pronounced fastness to washing and tulling of the products claimed is particularly worth mentioning. By suitable substitution they are 7 'cides, fungicides and insecticideaas excellent mere agents against blood parasites and agents passes over. The residue is received in one litre of'water and filtered hot; From the hot filtrate there separates on cooling the N-2'-(4"-'chloro- 2"-sulphobenzyl) -5'-chloro phenyl-N-Szd-dichlorophenyl urea, in white flakes. lhey are sucked off, washed with a little water and dried in vacuo. The yield isquantitative.

Instead of 3:4-dich1orophenylisocyanate there may be used i-chlorophenylisocyanate, t-chlorophenylisocyanate, 2-chlorophenylisocyanate, 4-,

methylphenylisocyanate, 2:4-dichlorophenyliso-' cyanate, 2:5-dichlorophenylisocyanata' 2:4:5- trichlorophenylisocyanate,3:4:5-trichlorophenylisocyanate. y

Examplev 4 l 1/20 moi. of 'm-aminobenzoyI-SM-dichIoroanilide-6-sulphonic acid edissolvedin 100 parts. by volume of dry pyri he, and thelsolution, whilst stirring and cooling, is treated slowly at l0 -'15 C. with 10 parts of 3:4-dichlorophenyl carbamic acid chloride. 5 Aiter introducing the product, a grey powder, dried in vacuo. is clearly f Q latter the whole is stirred for another 1% hours eral formula until the azo reaction disappears; Then it is treated with some soda. and the pyridine is blown ofl with steam. The residue is introduced into 1 litre of hot water, rapidly boiled, filtered hot and the filtrate is treated with brine. The condensation product is precipitated as a grey resin;

line filtrate obtained by means of hydrochloric acid. Instead oi. the 3:4-dichlorophenyl carbamic acid chloride may be used the corresponding isocyanate or also the compounds mentioned in the general part oi the description of this specification. I

' Example 5 31.5 parts ofd-chloro-f-amino-lz1'-diphenylketone-3-sulphonic acldare dissolved in 100 parts by volume of dry acetone and mixed while stir- The nitrocleus with a substituent selected from the group consisting of H, alkyl and halogen and It means a radical selected from the group consisting of the radicals (R--CH2-R') and a phenyl radical,

the whole molecule containing at least one BOJH group in one of the radicals R, R and Ft and at least one halogen atom in the same radicals R, R and Rhthese compounds being useful for durably protecting wool and other-substances quantity of 3:4-dichlorophenyl-isocyanic acid ester and further stirred at room temperature until there is no more free aminogroup'detectable with nitrite. After alkalinisation with a 10 per cent solution of soda the acetone is blown oil with steam, the residuals boiled up with two litres of water while steam is introduced thereinto, filtered hot and the condensation product is precipitated from the filtrate by means of acommon salt solution in form of a thick resin. The same is separated and dried in vacuo. The urea obtained in form of a colorless powder is well soluble in warm water.

What we-clalm is: 1. The urea derivatlves'of the following gen- I wherein R and'R' eachrepresents'a phenyl nuagainst moths.

2. The halogen substituted urea'oi the following formula BOtH being particularly useful for durably protecting ring at l0-'15 C. by portions with the calculated as W 01 and other substances against moths.

3. The halogen substituted urea of the following formula being particularly useful for durably protecting wool and other substances against moths.

HENRY MARTIN. HANS HEINRICH ZAESLIN. CURT GLA'I'IHAAR. man STAUB.

RUDOLF HIRT. 

